Progress in Organic Coatings 33 (1998) 91–100

Review Paper

Review of alternatives to chromate for corrosion protection of

aluminum aerospace alloys

R.L. Twite*, G.P. Bierwagen

Department of Polymers and Coatings, NDSU, Fargo, ND 58105, USA

Received 10 October 1997; accepted 9 February 1998

Abstract

The advent of chromate replacements for aluminum alloys began in the late 1970s. As regulations became increasingly stricter,
commercial, academic and government facilities have relied on a collaborative effort to come up with novel innovations for the corrosion
protection of aerospace aluminum alloys. More elaborate coatings formulations have failed to produce the level of protection that
chromates provide, therefore researchers have moved to more advanced technologies for improved protection. Some of the newer alter-
natives include low temperature cationic plasma deposition, sol-gel and ceramer coatings, various inorganic and organic inhibitors and
conducting polymers including some based on double helical structures. Although ultimate protection has not been achieved by one single
technique, it is believed that a combination of the most promising alternatives will provide the desired protection.  1998 Elsevier Science
S.A. All rights reserved

Keywords: Chromate replacements; Aluminum; Corrosion; Coatings

1. General background
This paper discusses the urgent need facing the aerospace
industry to replace the conventional corrosion inhibitor,
hexavalent chromium. Also discussed are the methods for
finding a suitable replacement for Cr6+ and the details of
expanding technology used to alleviate the concern of cor-
rosion for aluminum alloys. The current sciences used and
benefits and disadvantages of each procedure are acknowl-
edged. The contents are focused on the entire coating sys-
tem and can serve as an extension to a review on
replacements for chromium pretreatments written by
Cohen [1].
The aerospace industry places a high demand on the coat-
ings used to paint or repaint the existing aircraft fleet. Each
vehicle relies on several layers of coatings to provide
improved adhesion, protection against the environment
and corrosion, visual aesthetics and other specialized func-
tions such as low observability. A typical coating system is
comprised of three individual coating layers. The first layer,
a conversion coating, is the product of substrate pretreat-
* Corresponding author.
ment. The conversion coat is usually a very thin (,10–60
nm) inorganic layer that provides corrosion protection and
improved adhesion between the substrate and the primer,
which is the second layer of the coating system. The primer
provides similar functions to the conversion coat, but is
comprised of a pigmented organic resin matrix. The appli-
cation thickness of the primer can vary from 5 to 200 mm
although a thickness of 25 mm (1 mil) is typically desired
due to weight constraints on the aircraft. The primer is the
principal provider of corrosion protection. Typical formula-
tions consist of both chromated and non-chromated pig-
ments enveloped in an epoxy resin. Finally, a top coat is
applied which serves as the main barrier against environ-
mental influences such as extreme climates and ultra-violet
rays and it provides the aircraft with decoration and camou-
flage. A typical top coat is formulated using a polyurethane
resin and the application thickness varies from 50 to 200
pm. The complete coating system, as shown in Fig. 1, con-
sists of the pretreatment/primer/topcoat.
Recently, much interest has been focused on developing
new technology concerning the formulation and application
of the conversion coat and primer layers. To date, these
layers are formulated with corrosion inhibiting compounds

0300-9440/98/$19.00  1998 Elsevier Science S.A. All rights reserved

PII S0300-9440 (98 )0 0015-0
92 R.L. Twite, G.P. Bierwagen / Progress in Organic Coatings 33 (1998) 91–100
that contain hexavalent chromium. Hexavalent chromium,
or chromate, is currently the most effective way to inhibit
corrosion of aluminum alloys. Yet, the use of chromates and
other chromium containing compounds has been limited
since 1982 due to their carcinogenic effects. The Environ-
mental Protection Agency (EPA) is the main regulator of
chromate uses and emissions through several different acts
including the Clean Water Act, the Comprehensive Envir-
onmental Response, Compensation and Liability Act
(CRCLA) and Toxic Substances Control Act (TSCA) [2].
National emission standards for hazardous air pollutants
(NESHAP) were proposed for chromium along with 188
other hazardous air pollutants (HAP) listed in the Clean
Air Act. Within the military installations, Cr6 + is a Group
II compound on the Aeronautical Systems Center (ASC)
hazardous material priority list. The list was set up to iden-
tify hazardous materials and group them by their environ-
mental threat. Group II compounds have been designated to
be reduced and eventually eliminated [3]. Unfortunately,
the same properties that make Cr6 + a superior corrosion
inhibitor also make it environmentally unsafe. It is the
strong oxidation properties of chromates that have brought
much scrutiny concerning their use. It appears that Cr6 +
does not intimately react with human DNA, but instead
goes through a reduction to Cr5 + which eventually is
responsible for the DNA damage [4]. Chromate exposure
is primarily through inhalation, ingestion and skin contact.
The most common ailment is lung cancer, but the toxicolo-
gical effects are not limited to cancer alone [2]. Although
there is speculation that eventually chromates will be com-
pletely banned from use, the current legislative trend is
following the same path as volatile organic compounds
(VOCs) in that they will be significantly reduced, but not
eliminated [5].
The economic and environmental burden of using chro-
mates has dramatically affected the aerospace industry due
to its dependence on the use of aluminum based alloys in
aircraft manufacturing. Environmentally, the industry must
deal with lower limits of exposure to workers along with
controlled release and clean-up of by-products and waste
generated by its use. The latest NESHAP mandate, June
1994, was set up to reduce aerospace industry HAP emis-
Fig. 1. Schematic of components that make up an aircraft coating system.
sions by 123 700 tons. There is a direct economic challenge
associated with costs for environmental compliance along
with increased liability for claims of exposure in the work-
place. The current public health service exposure limit for
chromium is set at 0.05 mg/l [6]. Indirectly there is an
economic burden of allocating finances toward research
and production of new materials and technologies in order
to find a suitable replacement for chromium.
Since the federal mandate on the control of chromate
containing compounds, much collaborative work has been
done in the academic, industrial and governmental sectors
to find a suitable method for corrosion control of aluminum
based alloys. The most common alloys studied are an alu-
minum/copper alloy, Al-2024 and an aluminum/zinc alloy,
Al-7075. In order to determine how to protect an active
metal from corrosion, the fundamental aspects of degrada-
tion must be known. Currently, the exact mechanisms gov-
erning corrosion of aerospace aluminum are not completely
understood. In general, corrosion of a metal proceeds when
five conditions are met. An active corrosion site consists of
an anode, cathode, continuous electrical contact between
the anode and cathode, continuous electrolyte and a catho-
dic reactant such as O2, H2O or H2. The electrochemical
equations governing the corrosion of aluminum when
alloyed with copper or zinc (Al-2xxx and Al-7xxx series,
respectively) are:
Al → Al3 + + 3e − (1)
O2 + 2H2 O + 4e − → 4OH − (neutral=alkaline) (2)
2H + + 2e − → H2 ↑ (acid) (3)
The ease of reactions 2 and 3 on the alloying metal and the
galvanic coupling effect greatly increases the rate of corro-
sion for aluminum. Contact of the alloy with water and
oxygen or hydrogen completes the galvanic cell such that
oxidation of the metal takes place. Since an alloy has the
anodic and cathodic sites (copper inclusions) in constant
electrical contact, the only way to inhibit corrosion is to
eliminate the contact with electrolyte and the cathodic reac-
tant. The main methods to prevent such corrosion are by
using organic or inorganic barrier coatings and by using
 R.L. Twite, G.P. Bierwagen / Progress in Organic Coatings 33 (1998) 91–100 93

passivating inhibitors (Fig. 2). The barrier coatings are used

to suppress the cathodic reaction by limiting the diffusion
of the electrolyte, oxygen and water to the substrate. It also
limits the transport of electrons to the metal interface. Pas-
sivating inhibitors such as chromates, work in a similar
manner except that they operate under site-specific condi-
tions. These inhibitors undergo reduction at the active cor-
rosion sites (grain boundaries, inclusions, pits or
precipitates) to form insoluble oxides which deposit and
provide a barrier to further permeation of water, oxygen
or electrolyte. The formation of a barrier layer from the
active inhibitor that covers either the entire surface or
just the corrosion site will limit the permeability of electro-
lytes (chloride ions) and water, therefore reducing the rate
of corrosion. Complete protection is often obtained by
combining a cathodic inhibitor with a barrier coating.
Chromates as active inhibitors are being replaced by other
components such as cerium and molybdate compounds.
Advanced resin application methods are being used to
replace chromates by providing a more coherent barrier
layer with the underlying interface. These applications
include methods such as vapor deposition and electrodepo-
sition. Sol-gel coatings and conducting polymers are being
developed as new resin systems for corrosion protection.
Also, there is a broad range of aluminum surface modifica-
tion techniques that are under investigation. Although, to
date there has not been a singular successful candidate for
chromium replacement, it is hoped that the combination of
the different techniques and compounds listed above will
provide the protection desired.

2. Chromate replacement inhibitors

An organic coating alone is not sufficient to protect an
underlying metal substrate from corrosion. In general a
coating contains micro-pores, areas of low cross-link den-
sity or high pigment volume concentration (PVC) that pro-
vides a path for diffusion of corrosive agents such as water,
oxygen and chloride ions to the coating/metal interface.
Therefore, it is most often necessary to incorporate inor-
ganic or organic inhibitors into a paint system for corrosion
protection. The most effective corrosion inhibitor in use is
hexavalent chromium (Cr6 + ).
Chromates have been around since the early 1900s as a
means to control the corrosion of active metals [7]. Cur-
rently they are used to protect industrial ferrous and non-
ferrous alloys. They are employed into the coating system
through pigmentation (strontium chromate (SrCrO4) or zinc
chromate (H2CrO4Zn)), chromate conversion coatings or
chromic acid anodization (H2CrO4) of the alloy substrate
[8]. A chromate conversion coating is a chemically grown
oxide layer on the alloy substrate that provides an active
barrier layer that reduces the rate of the cathodic oxygen
reaction. The coatings are typically formed at pH between
1.5 and 3.0. The electrochemical reactions for the conver-
Fig. 2. Schematics for (A) corrosion cell for Al-2024-T3 and (B) aluminum
alloy protected by a barrier coating.
sion coating processes are well known and can be found in
Ref. [9]. The final result is a 10–60 nm thick film consisting
of Cr(OH)3 and A1(OH)3. Chromic acid anodization on the
other hand involves the electrochemical growth of an oxide
layer where a thin non-porous oxide layer is formed with a
thicker porous layer on top of it. The thickness of the ano-
dized layer is dependent on the applied voltage during film
growth, but is usually 0.05–0.1 mil (1 mil = 25 mm) thick
[10]. Chromates are introduced in the final stage of anodiza-
tion by sealing the porous layer with chromic acid (H2CrO4).
Thus, the thicker oxide layer provides barrier protection for
the bare metal as well as providing active passivation.
Despite the superior corrosion protection offered by anodi-
zation, conversion coatings are preferentially used due to
economic benefits. Anodization can be quite expensive
and therefore not affordable or practical when dealing
with large aluminum structures.
Aside from the pretreatment, chromates are commonly
used as pigments in the primer coating. A typical formula-
tion is given in Table 1 [11].
Chromated primers provide active passivating character-
94 R.L. Twite, G.P. Bierwagen / Progress in Organic Coatings 33 (1998) 91–100
istics through uniform pigment distribution. These chro-
mated pigments are slightly soluble in water allowing
them to diffuse to active corrosion sites. Often, both a chro-
mate conversion coating and a chromated primer are used in
the total coating system. Twite and Bierwagen observed a
minor difference in corrosion protection between chromated
primers applied to substrates with and without a chromate
conversion coating [13]. The amount of chromate in the
primer matrix from the pigments provided sufficient protec-
tion for the untreated alloy.
In the search to find a promising replacement inhibitor for
chromate, a mechanistic approach was taken by Kendig et
al. to identify the characteristics of Cr6 + that make it an
effective inhibitor [14]. Chromates are used due to their
strong oxidizing powers, their solubility in water, the pas-
sive nature of their reduction products, and their cost and
ease of application. The exact mechanism for corrosion
inhibition by Cr6 + is still being debated, but it is accepted
that the solubility of Cr6 + in water aids in its transport to
actively corroding sites where it passivates the area by redu-
cing to Cr3 + [15]. Among the most promising candidates
being investigated as active inhibitors are cerium com-
pounds, molybdates, vanadates and phosphates. Section
2.1 outlines the highlights from the most recent research
conducted concerning these active inhibitors.
2.1. Cerium compounds
Some of the most promising chromate replacement inhi-
bitors are derived from cerium salts [16]. They are believed
to control the cathodic reaction by precipitating cerium
hydroxide (Ce(OH)3) at local regions of high pH [17]. Aldy-
kiewics et al. studied the effects of cerium chloride on Al–
2024-T3 using in situ current density mapping. They con-
cluded that there was a preferential Ce deposition over the
copper rich regions which was associated with increases in
pH due to O2 reduction [18]. Wang and Mansfeld modified a
process that incorporated cerium which was originally intro-
duced by Hinton to inhibit corrosion of high strength alu-
minum alloys [19,16]. The process involves immersion of
the alloy in hot Ce(NO3)3 followed by anodic polarization in
Na2MoO4 and final immersion in hot CeCl3. Polarization
Table 1
Formulation of a two-part epoxy primer for aircraft (meets specifications
for MIL-P-2377) [12]
Part A wt.% Part B wt.%
Strontium chromate and 37.5 Polyamide resin 31.6
other pigments
Epoxy resin 22.9 Glycol ether 15.0
Additives 0.2 Toluene or xylene 54.4
Methyl isobutyl ketone 21.0
Xylene 7.6
Toluene 10.8
Total 100.0 100.0
curves of surface-modified samples immersed in 0.5 N
NaCl where reported to have pitting potential (Epit) values
200 mV higher (more noble) than the untreated samples.
The increase in Epit is indicative of the system reaching a
more noble state. The process yielded excellent corrosion
resistance for the Al-7000 series and marked improvements
for the Al-2000 series using this process. Cerium com-
pounds are also being incorporated into sol-gel coatings
systems, which are new candidates for aluminum pretreat-
ments and primers [20]. The sol-gel process is an emerging
technology used to produce thin metal oxide films at much
lower temperatures than traditional ceramic coatings [21].
Knobbe and Parkhill found increased corrosion resistance
with a layered combination of Ce(III)-doped SiO2/SiO2
epoxy thin films when compared with chromated Alodi-
ney conversion coats on Al-2024-T3 in 3% NaCl solution.
Although the reported cerium compounds show promise as
effective corrosion inhibitors, little has been mentioned
about their toxicity.
2.2. Molybdenum compounds
Molybdates have been tested extensively as possible
chromate replacements due to their oxidizing power and
stability of their reduction products, which form a passivat-
ing layer. As with chromates, molybdates are used as addi-
tives in conversion coatings or primer systems. Polarization
studies by Breslin et al. compared the effects of Na2MoO4
with Na2Cr2O7 on aluminum alloys in NaCl solutions [22].
They postulated formation of Mo, Mo3 + and MoO2 species
followed by the formation of molybdenum oxides with dif-
ferent oxidation states. The effectiveness of the molybdate
solutions was reported to be inhibited by the size and solu-
bility of the oxide MoO2 species. Sporadic pitting potentials
of .100 mV led to the conclusions that the oxidizing power
of MoO24 − was not as strong as the dichromate species
(Cr2O27 − ) and the molybdate species was too large to accu-
mulate at flawed areas, therefore unable to effectively pas-
sivate the region. Further studies by Breslin et al. found that
the pitting potential with molybdate inhibitors was more
dependent on the concentration of the chloride ion, and
was less dependent on the pH of the solution. Others also
reported the concentration dependence of the initial molyb-
date species and its effect on corrosion protection. Shaw et
al. indicated that lower concentrations seem to provide more
passivation protection than higher concentrations. They also
reported the presence of Mo4 + , MoO24 − and MoO3 species in
the passive regions [23].
Kendig et al. later reported an increase in the absolute
value of the Epit of Al-2024-T3 when using various blends of
zinc phosphate/molybdate powder dissolved in a 0.01 M
NaCl solution [24]. Monticelli et al. tested the effects of
different inhibitor solutions, including molybdates, on the
corrosion of aluminum using the power spectral density
(PSD) of electrochemical noise analysis (ENM) [25]. PSD
analysis proved to be an effective method to determine not
 R.L. Twite, G.P. Bierwagen / Progress in Organic Coatings 33 (1998) 91–100
only the effectiveness of the inhibitor, but also provided
some understanding of the mechanisms of the inhibitor.
They found that molybdates act as oxidizing inhibitors,
and the main inhibiting effect was due to an adsorbed
layer acting as a barrier to chloride ions.
2.3. Phosphates
Zinc phosphates were the initial replacement pigments
for zinc chromates. They display no toxic effects and pro-
vide some corrosion protection to aluminum alloys by form-
ing a Zn3(PO4)2⋅4 H2O film [9]. Bath composition typically
at pH 2–4 and consists of phosphoric acid, zinc dihydrogen
phosphate, fluoride and an oxidation accelerator such as
NO2.
Recently, MacQueen et al. [26] used electrochemical
impedance spectroscopy (EIS) to determine the corrosion
protection capabilities of several phosphate containing com-
pounds for Al-2024-T3. Of the ten compounds studied, cal-
cium strontium zinc phosphosilicate provided the best
protection under damaged conditions. They determined
the inhibition properties by ranking the data using Eq. (4):
(LogRinh − LogRcontr )
Rank =
LogRcontr
where R inh is the coating resistance value after 168 h of
immersion in 0.01 M K2SO4 and R contr is the coating resis-
tance value for a coating containing no inhibitors. The
ranking done by MacQueen and others was performed on
damaged (800 pm diameter hole) chromate conversion
coated Al-2024-T3. Therefore, effects of the chromate con-
version coating influence the exact inhibition properties.
2.4. Organic inhibitors
Organic corrosion inhibitors have been studied along side
the inorganic ones as possible chromate replacements. The
vast number of organic molecules and their derivatives have
allowed for a quite extensive survey of compounds. Most
organic inhibitors come in the form of weak acids and their
derivatives that form insoluble salts at the metal surface.
There have been some reports on chelating inhibitors that
formed an intimate bond between the organic complex and
the metal surface or its oxide [27]. The result was the crea-
tion of a thin (up to 20 nm) but tenacious passive layer.
Organic salts rely on the adsorption of the hydrophobic
anions to provide a thin barrier layer. Their effectiveness
can be correlated to the hydrophobic chain length and the
placement of carboxyl groups along the chain segment.
Jeffcoate investigated several corrosion inhibitors for post
mortem aluminum artifacts immersed in natural seawater
[28]. Solutions of sodium sebacate (NaOOC(CH2)8-
COONa), potassium hydrogen phthalate (C8H5O4K) and
sodium molybdate (Na2MoO4⋅H2O) were added to a solu-
tion of AlCl3 to test their effectiveness within a simulated
aluminum pit. The sodium sebacate solution (0.1 M) imme-
95
diately formed a thick white precipitate, while the other two
inhibitors did not. Electrochemical evaluation of the sodium
sebacate solution on fresh and already corroded aluminum
found it to function as an inhibitor to both pit nucleation and
pit growth as long as the chloride concentration remained
below 0.3 M. The mechanism for protection was not dis-
cussed. Raspini looked at the potentiokinetic effects of
sodium benzoate (NaC7H5O2), sodium acetate (NaC2H3O2)
and thioglycolic acid (HSCH2COOH) individually, and
combined, as inhibitors to pitting nucleation and growth in
NaCl solutions [29]. He found that the compounds effec-
tively stopped pit initiation, but were unable to stop pit
growth on the bare metal surface. His results were incon-
clusive about the mechanism for inhibition, but he postu-
lated a physico-chemical relation between the inhibitor and
oxide at the solution interface.
3. Barrier coatings
The chemical industry is quite aware of laws concerning
the release of volatile orrganic compounds (VOCs) and
other hazardous air pollutants (HAPs). Therefore, the repla-
(4) cement of chromates is shadowed by other environmental
concerns. Several of the barrier coatings that are being con-
sidered have been developed or modified specifically to
follow federal environmental regulations. Newer barrier
systems include plasma deposited coatings, sol-gel systems
and self-priming topcoats. Electrodeposition is also consid-
ered for aerospace application due to its successful use in
the automotive industry.
3.1. Plasma deposition
Low temperature cationic plasma deposition is currently
used to create ultra-thin hydrophobic barrier coatings on
metals. Plasma polymerized films with thicknesses of sev-
eral hundreds of nanometers boast high crosslink densities
with virtually, if not completely, defect free matrices [30].
The polymerizations are done in a dry atmosphere and the
process is within federal VOC regulations. Plasma coatings
have two invaluable properties for corrosion protection of
metals, which are a highly crosslinked matrix and excellent
adhesion to the metal substrate. Thus, the materials display
excellent chemical resistance and adhesion. The polymer-
ization method produces a highly crosslinked polymer film
that is also covalently bonded to the substrate surface. The
gaseous form of the monomer is ionized by passing it
through a DC current. The ionization promotes rapid step
growth polymerization (RSGP) by producing a reactive
intermediate which reacts with the metal ions at the sub-
strate surface [31]. Low temperature cathodic plasma
deposition of inorganic or silicon monomers have displayed
the best performance for corrosion protection with res-
pect to steel substrates immersed in simulated seawater
[32].
96 R.L. Twite, G.P. Bierwagen / Progress in Organic Coatings 33 (1998) 91–100
A combination of substrate cleaning and polymer deposi-
tion steps are generally used during the coating process.
They involve metal surface pretreatment or ‘cleaning’, inor-
ganic film deposition and composition-graded film forma-
tion [33]. The surface cleaning involves impinging either
oxygen or hydrogen and argon (H + Ar) ions at the metal
surface to remove any contaminants. The oxygen ions clean
the surface of its impurities and remove the original oxide
layer and a new ‘clean’ oxide layer is formed. The hydro-
gen + argon treatment removes the surface impurities and
oxide layer without forming a new oxide layer. Surface
cleaning and polymer film deposition are done consecu-
tively, therefore the risk of introducing new contaminants
or a fresh oxide layer, in the case of the hydrogen and argon
treatment, is minimized. As mentioned, silicon or organo-
metallic monomers may be polymerized and deposited via
cathode glow discharge to form the polymer film. However
a compositionally graded film can also be obtained by
applying a combination of sputter deposition of the metal
and organic monomer polymerization [34]. Cho et al. and
Schreiber et al. [35,36] have found improved corrosion pro-
tection from plasma polymerized thin films on steel sub-
strates. Yasuda et al. [37] are currently working on
optimizing a polymer system for the protection of aluminum
substrates. EIS results of a plasma polymerized tetra methyl
silane coating versus an Alodiney treated aluminum alloy
are shown in Fig. 3.
The modulus |Z| at low frequency is an indication of
the barrier resistance of the coating. The plasma treated
sample shows improvement by one order of magnitude
over Alodiney treated surfaces after 7 days exposure to
dilute Harrison’s solution. The coating resistance values
were determined using a Rebar equivalent circuit model.
The Rebar model consists of two embedded RC (resis-
tance/capacitance) circuits representing the ‘coating’ layer
and the ‘coating’/metal interface [38]. The circuit is shown
in Fig. 4. The double layer capacitance and polarization
resistance are labeled as Cdl and R p, respectively. The coat-
ing capacitance and coating (or pore) resistance are labeled
as Cc and R po, respectively.
The respective coating resistance values were 1.58 ×
103 ± 32.0 Q cm2 for the plasma treated alloy and 4.8 ×
102 ± 1.8 Q cm2 for the Alodiney treatment. The resistance
Fig. 3. Bode plot for plasma-treated and Alodiney chromate conversion
coated Al-7075-T6 in dilute Harrison’s solution.
Fig. 4. Equivalent circuit diagram for the Rebar model.
values indicate that the barrier properties of the plasma
system give better protection than the passive chromium
hydroxide (Cr(OH)3) layer from the chromate conversion
coating.
3.2. Sol-gel
As previously mentioned, sol-gel processing is a method
in which thin oxide films can be deposited on a substrate at
much lower temperatures than traditional ceramic proces-
sing methods. A variety of metal alkoxides, salts or nitrates
can be used as precursors for the oxide synthesis [39]. Upon
deposition, the coating undergoes hydrolysis and condensa-
tion to form a continuous three-dimensional oxide matrix.
The oxide layer acts as an inert, hydrophobic barrier layer
The intrinsic stresses and processing conditions for one-coat
systems limit the film thickness to less than 1 mm. Film
thickness of .1 mm can be obtained by combining additives
into the sol-gel or by creating multi-coat systems. Due to the
limited film thickness, sol-gel coatings are used as the sub-
strate pretreatment.
Much of the initial work concerning corrosion protection
offered by sol-gels was conducted with steel substrates [40].
Sol-gel processed oxide films such as SiO2, ZrO SiO2/TiO2,
SiO2/A12O3 and B2O3/SiO2 have been tested as barriers to
corrosion induced by high temperature, atmospheric expo-
sure, H2SO4 attack or concentrated electrolyte immersion
[41–45]. They have all shown promise, but have been of
limited use due to poor interfacial adhesion, shrinkage and
oxidation of the substrate. Currently the sol-gel processing
is being pursued as an alternative to chromate inhibitors for
corrosion protection of aluminum alloys [46,47]. A more
comprehensive review of the use of sol-gel produced
metal oxides as protective films has recently been published
[48].
The US Air Force, in conjunction with the academic and
commercial groups, has developed sol-gel systems contain-
ing aluminum oxides, zinc oxides, silicon oxides, zirconium
oxides and a combination of these oxides. It has been found
that one of the major characteristics controlling the corro-
sion protection properties of the coatings is the film thick-
ness [42,45]. Though one would expect a thicker film to
provide better protection, the opposite is true for sol-gel
films due to the tendency for cracking to occur in single
coat films greater than 1 mm.
 R.L. Twite, G.P. Bierwagen / Progress in Organic Coatings 33 (1998) 91–100
A more realistic approach for defect free film formation is
being taken by combining the various metal oxides with
organic segments to form what are called ceramers. They
are synthesized using organic functionalized metal alkox-
ides that promote reaction between an organic group and the
inorganic alkoxide. Ceramer systems are potential chromate
replacements due to the ability to tailor the systems to the
specific needs of the user. The organic segment adds flex-
ibility to the system, which lowers the internal stresses of
the system and reduces shrinkage of the coating. Due to the
increased flexibility the coating thickness for ceramers is
higher than that for traditional sol-gel coatings which
expands their use.
3.3. Self priming topcoats
A chromate free coating system was developed by the
US Navy specifically for compliance with the mandates
against chromate use. This particular system is called a
self-priming topcoat (SPT) or a direct to metal (DTM) coat-
ing. As the name implies, the system provides both primer
and topcoat functions with just one coating layer. A self-
priming polyurethane was first developed by the Navy for
use with the current military aircraft fleet. Published results
indicated superior performance over the traditional epox-
y(primer)/polyurethane(topcoat) multi-coat system [49].
Both barrier and inhibitive mechanisms provided corrosion
protection. The inhibitors were comprised of a combination
of three non-toxic corrosion pigments, zinc molybdate (two
parts), zinc phosphate (one part) and zinc benzoate (0.1
parts) [50,51]. Others have not seen some of this corrosion
protection. A self-priming topcoat was one of many sys-
tems tested by the Air Force for corrosion protection of
Al-2024-T3. The system provided only fair protection,
comparable with military specification aircraft primers
[52].
3.4. Electrodeposited coatings
An environmentally friendly system that has been proven
effective by the automotive industry is electrodeposition of
organic resins (e-coat). Electrodeposition has been commer-
cially available since the 1960s when the first patent was
issued to the Ford Motor Company [53–55]. The unique
advantage of electrodeposition is that a thick (up to several
mm) coating can easily be deposited on a conducting sub-
strate with good control of the thickness. A semi-uniform
and continuous film with excellent interfacial adhesion is
achieved, even in less accessible areas due to the high
throwing power of the method. The deposition process
can be modified to undergo either cathodic or anodic deposi-
tion depending on the resin functionality [56]. Cathodic
deposition is predominantly used today for corrosion appli-
cations because of some inherent disadvantages of the ano-
dic process. With cathodic electrodeposition, oxidation of
the resin and electrochemical dissolution of the metal
97
become insignificant factors. Several types of resins have
been successfully used for e-coat binders. These binders
include acrylics, alkyds, epoxies, polyurethanes, polya-
mides and polyesters [57]. Electrochemical evaluation of
e-coat systems has been used to demonstrate its excellent
barrier properties [13,58]. Twite and Bierwagen [13] pre-
sented data showing the superior barrier protection beha-
vior of polyurethane/blocked isocyanate e-coats on
aluminum alloys with and without a chromate conversion
coat pretreatment. Accelerated weathering from Prohe-
siony exposure indicated that the conversion coat was
necessary to protect damaged areas, but the coating main-
tained excellent barrier properties away from the damaged
area. The ability to produce sufficiently thick coatings
allows e-coats to be used as a primer or one-coat system.
More often they are used as primers due to resins that have
poor weatherability resulting in loss of gloss and color.
However, some epoxy based (blocked isocyanate) resins
are used quite extensively as stand alone coatings due to
their good weatherability [59].
4. Conducting polymers
The use of conducting polymers such as polyaniline (I)
and polypyrrole (II) as corrosion protection systems has
emerged in the past decade [60–62]. Much of the initial
work concerns corrosion protection of mild and stainless
steels [63–65]. Effective corrosion protection is achieved
by conducting polymer systems when they are in the
doped or conducting form. The mechanism for protection
is not by barrier methods, but instead it is believed that the
polymers aid in the formation of a passive oxide film at the
metal surface through an anodization process. Despite the
good corrosion protection abilities of conducting polymers
thus far reported, their main disadvantage lies in thin film
processing. The application process involves either electro-
polymerization in a acid media or casting the non-conduc-
98 R.L. Twite, G.P. Bierwagen / Progress in Organic Coatings 33 (1998) 91–100
tive form of the polymer from solution and then converting
it to its conducting state. Unfortunately, the structure of the
doped material is unstable and therefore susceptible to loss
of conductivity.
Of the various systems tested, a double stranded polyani-
line based polymer synthesized by Liu and Yang shows
excellent characteristics as a possible replacement for chro-
mate systems [66]. A group from the University of Rhode
Island has been studying the double helix form of polyani-
line as a possible corrosion protection system for aluminum
based alloys [67–69]. The polymer is referred to as PAN/
PolyE, designating use of both the polyaniline segment and
the polyelectrolyte segment. The polyelectrolyte is a car-
boxylic acid modified vinyl co-polymer. The acid groups
serve as the dopants for the material and therefore the mole-
cule remains stable in the conductive form. The corrosion
current density of a treated sample is almost two orders of
magnitude lower than that of an untreated system. The
PAN/PolyE treated samples were compared with chromate
conversion coated samples immersed in 0.5 M NaCl [68].
The EIS and polarization measurements were similar for the
two systems. Salt spray immersion was also done and the
polyaniline system showed little or no (negligible) disbond-
ment from the scribe and no corrosion was visible away
from the scribe [68].
Due to the poor processibility of conducting polymers
such as polyaniline into coatings, it has been postulated to
use the polymer as a pigment or other resin additive.
5. Surface modification
Sections 3 and 4 were concerned with the application of a
coating to impede or suppress the corrosion process. This
was accomplished by applying either a barrier coating or a
reactive inhibitor that will subsequently form a site-specific
barrier layer. Instead of applying a coating, one can modify
the metal surface to create a conversion layer. Conversion
layers provide the ability to modify the aluminum surface to
give better adhesion, a surface free of contaminants or a
coating layer that contains active corrosion inhibitors. Con-
version layers can be created through a variety of techniques
which include physical vapor deposition, cathodic magne-
tron sputtering, high energy ion beams and laser ablation
[70–72]. The most common conversion layers are from
electrochemical anodization, plasma ablation and chromate
conversion coatings and modifications thereof.
5.1. Anodization
As mentioned earlier, a thick oxide layer can be elec-
trochemically grown on an aluminum substrate by anodic
oxidation (anodization). Electrochemical anodization of
aluminum is performed using the sample as the anode
immersed in 1.5 M sulfuric acid with a steel cathode. As a
constant current density is applied to the electrochemical
cell, the aluminum panel undergoes oxidation, reacts with
water and forms aluminum oxide, as shown in Eq. (5).
2Al(s) + 3H2 O(l) → Al2 O3 + 6H + + 6e − (5)
Typically a tenacious and dense oxide layer is formed
immediately at the surface with a more porous outer
layer. The outer oxide layer is 99% porous with the pores
reaching approximately 20 nm from the aluminum surface
[73]. The oxide is usually ‘sealed’ with the boehmite struc-
ture (Al(OH)3) of aluminum hydroxide by immersing the
sample in boiling water (80–100°C) or NaOH. The pores
can also be sealed with a inhibitor such as chromic acid or
other active inhibitors to help with corrosion protection.
The thickness of the anodized layer is dependent on the
applied current, the voltage and the length of application.
The properties of the oxide layer are affected by the nature
and composition of the electrolyte and by the aluminum
substrate [74].
The electrochemically grown oxide layer provides extra
barrier protection due to the highly capacitive behavior of
Al2O3. This behavior is easily demonstrated by comparing
the electrochemical impedance spectra of uncoated Al-
2024-T3 alloy with and without anodization treatment.
The log modulus versus log frequency plot from an EIS
scan of Al-2024-T3 bare and Al-2024-T3 anodized after
60 min in 3% NaCl is shown in Fig. 5.
Oxide resistance values were evaluated using a Rebar
equivalent circuit model shown previously in Fig. 4. The
values obtained were 9.9 × 103 ± 50.0 and 7.3 × 102 ± 4.0
Q cm2 for the anodized and bare samples, respectively.
Polarization measurements also show the improved perfor-
mance of the anodized sample with a several order decrease
in the corrosion current density with respect to the untreated
sample.
5.2. Plasma ablation
Surface cleaning by plasma ablation was discussed
briefly in Section 3.1. A more in depth account of plasma
polymerization and plasma ablation was written by Yasuda
[30]. Plasma ablation takes place by one of two methods,
sputtering or chemical etching. Sputtering is used to remove
organic contaminants and oxides from the metal surface.
The surface is cleaned by bombarding it with an inert gas
plasma. Argon and hydrogen are used extensively for this
procedure. As the gas ion collides with the surface, an
energy exchange takes place, which dislodges the atoms
at the surface leaving it free of organic and inorganic con-
taminants and inhomogeneities. Chemical etching involves
chemical reaction between the impinging ion and the dis-
lodged atoms. Oxygen is used with chemical etching to
‘clean’ the surface of a metal as well as deposit a synthetic
oxide layer. The energy and quantity of oxygen control the
properties of the oxide layer. Therefore, the etching rate is
dependent on the discharge power and oxygen flow rate to
the system. The biggest difference between sputtering and
 R.L. Twite, G.P. Bierwagen / Progress in Organic Coatings 33 (1998) 91–100
Fig. 5. EIS bode plot for bare and anodized Al-2024-T3 in 3% NaCl.
chemical etching is the change in the surface energy and its
effect on adhesion of coatings to the surface. Adhesion of an
organic paint layer to a metal surface is one of the fun-
damental aspects to acquire optimum corrosion protection
for any metal. Therefore, by providing a conversion layer
with higher surface energy between the metal surface and
organic layer, better corrosion protection will be achieved.
Otherwise when using chemical etching with oxygen the
creation of an oxide layer thicker than the natural oxide
present will provide more barrier protection at the metal
interface.
6. Summary
The heavy restrictions on the use and disposal of chro-
mate containing materials has lead to an exhaustive search
to find a suitable replacement for them. Several alternative
processes which can be used throughout the coating system
to provide improved corrosion protection of aluminum
alloys have been presented. The main methods for corrosion
protection are through inhibitors and barrier coatings,
although alternative surface preparation techniques have
been evaluated in order to achieve optimum adhesion.
Most of the candidates discussed have been successful in
development, but no single alternative has proven itself as
reliable as chromate for corrosion protection. A combina-
tion of surface treatment, barrier coating and inhibitor is
most likely to succeed. Of the methods presented, the
most promising include cerium based inhibitors, ceramer
coatings and electrodeposition coatings, although most are
still in either research or development phases rather than
commercial use. Future trends are predicted to be directed
towards conducting polymers and variations of sol-gel sys-
tems applied with traditional, low VOC organic primers.
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